Rubber vulcanizates and process of preparing same



. inner tubes, rubber thread and United States Patent RUBBER VULCANIZATES AND PROCESS OF PREPARING SAME No. 462 623. Divided and this li a A .23

1957, Se No. 680,379 app ca on 6 Claims. (Cl. 260-453) This invention relates to inhibiting or retarding the deterroratmg action of ozone on rubber by new chemical compounds. The new chemical compounds and their production are disclosed and claimed in my application Serial No. 462,623, filed October 15, 1954, of which this application is a division. r The rubber compositions may be those used in tires, other products, including products obtained from latexes. The compositions consist essentially of vulcanizates of hydrocarbon diene rubbers, for example natural rubber or a sulfur-vulcanizable synthetic rubber as, for instance polymer of butadiene or an alkyl derivative thereof, or a copolymer of butadiene or an alkyl derivative thereof with a vinyl como-nomer, or a mixture of sulfunvulcanizable rubbers.

The inhibitors belong to the general class of trisubstituted phenylenediarnines or, more particularly, the reaction products of alkylene dihalides of 1 to 8 carbon atoms with orthoand para-phenylenediamines having the formula:

in which R R and R are each from the class consisting of alkyl, cycloalkyl, alkylcycloalkyl, hydroxyalkyl and hydroxycycloalkyl groups containing 1 to 20 carbon atoms, with the proviso that when R and R are joined as an alkylene group the alkylene group contains 2 to 10 carbon atoms. These reaction products are obtained by reaction of 2 mole o the. phenylenediamine with one mole of the alkylene dihalide and are of the three general types, as will be more fully explained in what follows.

The deterioration of rubber is due to various factors and is evidenced in diiferent ways. The inhibitors of this, invention have been found to absorb or destroy ozone and thus prevent or inhibit its. deteriorating action on rubber.

Oxygen and ozone both have a harmful effect on rubber, but the effect of each is different, and compounds which inhibit or prevent the harmful efiect of one are not necessarily elfective in stopping the harmful effect of the othe Crabtree and Kemp in an article in Industrial and Engineerjng Chemistry, vol. 38, starting at page 278 (19:46), explain the difference in the the action of oxygen and ozone. The lighbcatalyzed oxidation which occurs d-u ing outdoor exposure forms a skin and crazed appearance over the exposed surface of the rubber. Ozone, even in very: low concentration, cracks stretched rubber only (C; Leigh-.Dugmore, Rubber Age and synthetics, N0,- Memher and December 1952), and forms cracks perpenthe. direction of stretch; such cracking can occur in the absence or light.

a matter of fact, nearly all commercial rubber oxidants are without effect in inhibiting the detera aw b r W 2,939,861 Patented June 7,

Natural rubber is used in the manufacture of the sidewalls of tires. The cracking of such sidewalls has long been a problem. It is a primary object of this invention to provide 'antiozone agents which prevent such cracking. However, the antiozone agents of this invention are not limited to that use but may be employed in treads, thread and other latex products, and other rubber products.

Tires are stressed when inflated. While a tire is at rest it is stretched statically, and on a moving vehicle it is stretched dynamically, i.e., it undergoes alternating stretching and relaxation. Some of the antiozone agents are more efiiective in static tests and others are more etfective in dynamic tests. Antiozone agents effective under both conditions will be desired for tires, but for other rubber products an antiozone agent which does not meet both tests may be used.

The inhibiting eifect of the antiozone agents in rubber was determined by treatment of unaged, cured stocks with air of controlled ozone content in specially designed equipment and also by outdoor exposure to natural weathering. The tests recorded herein were conducted with one-half inch dumbbell samples of approximately 100 gauge thickness. The special apparatus for testing with air of controlled ozone content and the method of testing therein are described in the articles by Ford and Cooper, appearing in India Rubber World for September and October 1951, entitled A Study of the Factors Afiecting the Weathering of Rubber-like Materials-*1 and II. The following reports of such tests give the ozone concentration maintained during each test at 60 parts per 100,000,000 parts of air, for 7 hours at F. Two types of tests were conducted. In one type-called the dynamic test-the sample was repeatedly stretched between the limits of 0 and 20 percent elongation atthe rate of 108 cycles per minute. In the other type of testthe static test-the samples were stretched at 12.5 percent elongation throughout the test. A combined dynamic and static test was used in obtaining the data reported in Table 1. No special lights were used in either test. On completion of each test the size of the cracks in each sample was compared visually with the size of the cracks in a blank which contains no antiozone agent and which was cured and tested at the same time as the test sample. The size Was determined according to an arbitrary scale of measuring, with recordings of-very slight, slight, moderate, severe, and very sevcref and the frequency was recorded as very few, moderate, moderate-to-numero us, and numerous.

The natural rubber stocks mentioned in the following tests were cured 45 minutes at 280 F., and the GR-S r stocks were cured 60 minutes at 280 F. The reported results include data on the tensile properties of the cured rubber stocks before and after aging 2 days in an oven at {212 F. The modulus and tensile strength are given in pounds per square inch and the elongation is reported as percent of stretch at the break. These data are included to show that the antiozone agents have no substantial deleterious effect on the cure or upon the aging of the cured stocks. The formulae for the various test materials. are given in parts by weight.

In all of the test samples, both those tested in the special apparatus and those subjected to natural outdoor weathering, 2.0 parts by weight of the antiozone agent was added to the blank formula for each parts by weight of the rubber present. Any substantial small amount may be employed, and this may vary, for example, from 0.2 part by weight to parts by weight, depending upon the use to be made of the rubber composition.

PREPARATION OF THE ANTIOZONE AGENTS In carrying out the reaction of the alkylene dihalide with the phenylenediamine the halide can react with either the disubstituted or the mono-substituted amino group of the phenylenediamine, or one of the halogens can react with one of the amino groups and the other halogen can react with the other amino group. Thus, we have the following general types of reaction products illustrated by reference to the reaction of either an alkylene dichloride or an alkylene dibromide with a. trisubstituted orthoor para-phenylenediamine:

( ype 1) R2 R2 In the above formulas X is chlorine or bromine and the Rs are as identified in the general formula, above, for the trisubstituted phenylenediamines.

The products of Type 1 are solid and insoluble or sparingly soluble in benzene. The products of Type 2 are liquid and readily soluble in benzene. It appears that when R is methyl the Type 1 reaction proceeds much more rapidly than Type 2.

COMPOUND A Reaction product of N,N-dimethyl-N'-cyclohexyl-pphenylenediamine Two products were obtained in this reaction, designated A1 and A2, which are representative of reaction Types 1 and 2, respectively.

One-tenth mole (21.8 g.) of p-cyclohexylaminodimethly-an-iline was dissolved in 10 ml. of benzene and 0.054 mole of ethylene dibromide. After standing three weeks at room temperature 16 grams of crystals had separated and were filtered off.

COMPOUND A1 The crystals from Example 1 were washed with benzene and air dried. The substance melted gradually between 156 and 172 C. 'Itwas soluble in cold methanol; insoluble in benzene and water.

Analysis-BL: Found, 25.43; 25.22. Calculated for ethylene bis-(p-cyclohexylaminophenyl dimethyl-ammonium bromide) 26.6.

COMPOUND A2 The filtrate from Example 1 was heated to reflux on the steam bath with sodium carbonate solution approximately 6 hours, filtered, and the solvent distilled off in vacuo. The residue was in black oil, somewhat solu- Me in benzene. Molecular weight (cryscopic) found: 340. Calculated for N,N'(p-dimethylaminophenyl)- N,N'-dicyclohexyl-ethylenediamiue: 464.

COMPOUND B 5 N,N-(gamma-hamylpentamethylene) -N'-i-propyl-p- The tarry materail obtained was shaken with ether and benzene, in which it was partially soluble. The two nonaqueous phases were combined and the solvent distilled off.

The product has the formula COMPOUND C Ethylene bis(p-undecylamin0phenyl dimethyl ammonium bromide) One mole of N,N-dimethyl-N'-undecyl-p-phenylenediamine was mixed with 0.54 mole of ethylene dibromide and allowed to stand for two weeks. Thereafter it was heated on the steam bath for two and one-half hours. The product was a viscous, toluene-soluble syrup with a molecular weight Of 1144, probably mostly of Type 1.

COMPOUND D N,N-di-i-propyl-N,N'-di (p-dibutylaminophenyl) trimethylenediamine One-tenth mole of N,N'-dibutyl-N-i-propyl-p-phenylenediamine with 0.05 mole of trimethylene dibromide was stirred and heated on the steam bath with 0.05 mole of sodium carbonate in 50 ml. of water for 6 hours. The product was extracted with toluene, washed with water, dried over magnesium sulfate and the solvent distilled off. The residue had a molecular weight of 458. Analysis showed N=10.00, 10.02%. Calculated for N,N'- di i propyl-N,N-di(p-dibutylaminophenyl)trimethylenediamine, N=9.94%; molecular weight=564.

In the following tables, the antiozone agents are identified by letters, as Compound A, B, etc., as in the foregoing preparations. Other alkylene dihalides and trialkyl phenylenediamines can be used in producing antiozone agents, as, for example:

Alkylene dihalides Methylene dichloride and dibromide Ethylene dichloride and dibromide Propylene dichloride and dibromide Trimethylene dichloride and dibromide. Butylene dichloride and dibromide Tetramethylcne dichloride and dibromide Pentylene dichloride and dibromide Hexamethylene dichloride and dibromide Hexylene dichloride and dibromide Octylene dichloride and dibromide Methylethylene dichloride and dibromide Trialkyl phenylenediamines N,N-dimethyl-N-hexyl-oand p-phenylenediamines N,N-dimethyl-Neicosyl-oand P-phenylenediamines N,N-dimethyl-N-ur1decyl-oand p-phenylenediamines N,N-di-n-prOpyl-N'-cyclohexyl-O- and p-pheuylenediamines N,N-dimet-hy1-N'-ethyl-oand p-phenylenediamines N,N-dicyclOhexyl-N-methyl-O- and p-phenylenediamines N,N-diamyl-N-octyl-O and p-phenylenediamines N-methyl-N-ethyl-N'-i-propy1-O- and p-phenylenediamines N,N-dibutyl-N-sec-butyl-oand p-phenylenediamines N,N-diethyl-N'-sec-butyl-O- and p-phenylenediamines N,N-ethylene-N'- (4-hydrOxy-4-methyl-2-hexyl) -p-phenylenediamine phenylenediamine The two last-named alkylene derivatives of phenylenediamine are prepared by the procedures Outlined below. Ethylene dibromide is reacted with p-nitraniline, and the resulting condensate is reduced with iron and hydro.- chloric acid to N,N-ethylene-p-phenylenediamine; the latter compound is alkylated by reacting it with 2 molar proportions of 4-hydr0xy-4-methyl-2-pentanone ina mix: ture of ethanol and glacial acetic acid, in the presence of the Adams platinum oxide catalyst, and under hydrogen at a pressure of 2 to 3 atmospheres; thealkylation mixture is shaken until the pressure drop indicates absorption of one molar proportion of hydrogen. The second derivative is prepared, starting with gamma-i-amylpiperidine, produced by condensing gannnaepicoline with ibutyraldehyde and then reducing the condensate with hydrogen and a nickel catalyst; the piperid-ine derivative is condensed with p-nitrochlorobenzene, andthe condensate is reduced with iron and hydrochloric acid; the resulting N,N (gamma i-amylpentamethylene)-p-phenylenediamine is alkylated by reacting it with 2-molar proportions of acetone in the presence of hydrogen and the Adams catalyst, as outlined above. The other trisubstituted phenylenediamines mentioned above are each prepared from the appropriate known N,N-disubstituted phenylenedia nine by reaction with the appropriate ketone in the presence of hydrogen and the platinum catalyst.

The following test reports are given as illustrative of the effect of the antiozone agents refen'ed to herein. In the reports the reaction products are identified by the letters used in the several preparations.

TABLE 1 Control Test 1 100 100 4 4 3 3 3 3 A r-elevator 1 1 Sulfur 3 3 EP0 Black; 50 50 Wax 3 3 Compound B y 2 Total 167 169 Normal Properties:

400% Modulus 3, 000 2, 500 Tensile 3, 850 3, 725 'Elnn oat-inn 480 500 Properties Aiter Aging 2 Days at 212 F.:j"

Ten il 2, 075. 1, 575 Elongation 270 280 Ozone Test in Artificial Weathering Machine Combined Static and Dynamic Test: 1

Crack size Slight Slight Crack frequency Numerous Moderate The addition of Compound B reduced the number of ozone cracks in this stock.

TABLE 2 Control Test 2 Formula: 1

Smoked sheet 100 100 Oil soitener 4 4 Stearicacid- 3 3 Zinc oxide. 3 i 3 Accelerator 1 1 Sulfur 3 3 E190 Black. 50 50 Wax 3 3 m un 0 i 2 Total 167 169 Normal Properties:

400 odulus 2, 900 2, 750 Tensile 3, 850 3, 840 Elongation 480 510 Properties After Aging 2 Days at 212 F.:

Tensile l, 625 2, 400 'Flrm mitirm 270 320 Ozone fest in Artificial Weathering Machine:

a le- Orack size Moderate None Crack Frequency- Moderate Dynamic- Crack size Moderate Very slight Crack frequency Numerous Numerous The rubber vulcanizate containing Compound C showed improved resistance to ozone attack. In the static test it developed no visible cracks and only very slight cracks under dynamic conditions while the control vuloanizate developed moderate sized cracks under both static and dynamic conditions.

TABLE 3 Control Test3 Test 4 V 100 100 45 45 46 a a s 011 softener. 10 10 10 Su1iur 2 2 2 Accelerator- 1. 3 1. 3 1. 3 Compound B 2 Compound 0 2 Totalfllh 161. 3 163. 3 p p 163. 3

Normal Properties: 300 0dulus 1, 550 1, 450 1, 575 Te'nsile.- i, 760 1, 925 l, 575 Elongation- 320 380 300 After Aging 4 Day Tensil 1, 325 1, 500 i, 376 EIongat 190 I70 Ozone Test Ar lng Machine:

Static (12.5% elongation)- D V Crack Moderate Slight Slight Mod. to Moderate Mod. to Num. Num. Dynamic (0-20% elongation)-- Crack Sizer. Slight V. Slight V. Slight Crack Ir'equ Numerous N urii'erou's N umei-otis Ozone had less. efiect on the rubber strips containing P mQ B and C than onthe control stock containing no antiozone agent, 1 V

TABLE 4 Control Test 5 Formula G 100 100 EMF Black 45 45s Zinc oxide... 3 3 Oil sottener 10 1Q Sulfur 2 2 Accelerator l.-l. l.. 1. 3 l; 3 Compound Al i 2 Total. .-ll 1'61. 3 163. 3

Normal Propertiesi 300% modulus; "AA----'-..--LJ; 1, 425 1,325 T n i I t 2, 200 2, 275 Elongatiom; 440 490 After Aging 4 Days at 212 I Tensile l 1, 525 l, 475 Elongationuug 240 Ozone Test in Artificial Weathering Machine:

Static. (12}/% e1ongation) n Crack size Slight Crack frequency.- Numerous Dynamic. s-20%, elon n Crack size.. Slight g Greek frequency- A Numerous N umerons In both static and dynamic tests the rubber sample containing CompoundAl gave less evidence of ozone attack. In the static" test, ozone cracks'were absent from the strip containing the antiozone agent.

TABLE. 5

Control Test 5 Formula:

Total 161 3 163.3

Normal Properties:

300% Modulus 1, 450 1, 400 Tensile 1, 920 2, 140 Elongation 380 430 After Aging 4 Days at 212 F.:

Tensile 1, 625 l, 900 'Flnnn'atirm 200 240 Ozone Test in Artificial Weathering Machine:

Static (12%7 Elongati0n) Crack size Moderate Slight Crack frequency Mod. to Very Few D 2 7 El t I ynamic 0- 0 a onga ion Crack size Slight Very Slight Crack frequency Numerous Numerous Less severe cracking observed in the stock containing Compound D than in the control stock indicates that the added compound was an active antiozone agent.

'By sulfur-vulcanization is meant the curing of rubber by reaction with either free sulfur or a vulcanizing agent of the sulfur-donor type. Kno w'nflagents' of the latter type include the various phenol polysulfides including the alkyl derivatives thereof, the Xanthogen'fpolysulfides, the thiuram disulfides and polysulfides, various amine sulfides including the dialkylamine polysulfides and reaction products of primary amines with excess sulfur. Known .vu canization accelerators are useful in speeding up the vulcanization process and operative herein; especially the relatively active accelerators including the thiazole sulfenamides, e.g., N-cyclohexyl-Z-benzothiazolesrflfenamide, thiazoline sulfcnamides, .thiocarbamyl sulfenamides, mercaptothiazoles, mercaptothiazolines, thiazolyl monoand di-sulfides, the N,N-disubstituted dithiocarbamates, the thiuram sulfides, the xanthogen sulfides, and metallic salts of mercaptothiazolcs or mercaptothiazolines or dithiocarbamic acids. 7

One or more accelerator activators is often used with .any of the accelerators mentioned, and such activators include the various derivatives of guanidine known in the rubber art, amine salts of inorganic and organic acids, various amines themselves, and alkaline salts such as sodium acetate and the like, as well as other activators known in the art. Additionally, two or more accelerators or accelerator combinations are sometimes desirable in a single rubber compound. Many of the accelerators mentioned above are suitable in latex formulations, especially such common accelerators as piperidinium pentamethylene dithiocarbamate, zinc butylxanthate, zinc ethylxanthate, zinc salt of mercaptobenzothiazole, zinc dimethyldithiooarbarnate, and zinc dibutyldithiocarbamate. Although vulcanization is usually accomplished by heating a vulcanizable rubber composition at a temperature in the range of 240 to 400F. for a time ranging from several hour to a few seconds, vulcanization does take place at lower temperatures such as ordinary room temperature. It is quitecomrnon to vulcanize alatex film containing an ultra-accelerator by allowing the film to remain at room temperature for several hours or a few days;

What I claim is: y I

.1. The process of producing a vulcanizate which comprises sulfur-vulcanizing a sulfur-vulcanizable hydrocarbondiene rubber in the presence of a small amount of an antiozone agent which is from the class consisting of compounds having the formulae.

in which the phenylenediamine nuclei are from the class 'consisting of orthoand para-phenylenediamine nuclei; X is from the class consisting of chlorine and bromine; R and R when they occur asseparate substituents are 2. The process of claim 1 in which the rubber is natural rubber. I V 3. The process of claim 1 in which the rubber is a synthetic hydrocarbon-diene rubber.

4. Sulfur vulcanizate of a sulfur-vulcanizable hydrocarbon-diene rubber which contains a small amount of antiozone agent which is from the class consisting of compounds having the formulae in which the phenylenediamine nuclei are from the class consisting of orthoand para-phenylenediamine nucleif X is from the class consisting of chlorine and bromine; R and R when they occur. asseparate substituents are each from the group consisting of alkyl, cycloalkyl and hydroxyalkyl groups containing 1 to 20 carbon atoms,

and R and R when they occur as one substituent represent an alkylene group of 2.to 10 carbon atoms; R is from the group consisting of alkyl, cycloalkyl and hydroxyalkyl groups containing 1 to 20 carbon atoms; and alkylene represents an alkylene group of 1 to 8 carbon atoms.

is natural rubber.

6. A sulfur vulcanizate of claim 4 in which the rubber ber.

References Cited in the file of this patent UNITED STATES PATENTS S. A sulfur vulcanizate of claim' 4 in which the rubber,

is a sulfur-vulcanizable synthetic hydrocarbon-diene rub- UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No. 2,939,861 June 7, 1960 Joseph C. Ambelang It is hereby certified that error appears in the above numbered pat ent requiring correction and that the said Letters Patent should read as corrected below. I

Column 1, line 43, strike out "the", second occurrence; column 2, line 47, after '"very few, insert "few, column 3, lines 16 to 19, the formula for (Type 1) should appear as shown below instead of as in the patent:

same column 3, lines. 23 to 25, the formula for (Type 3) should appear as shown below instead of as in the patent:

H R X R R column 4, line 1, for "materail" read material column 7, line 39, for "hour" read hours Signed and sealed this 5th day of December 1961.

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents 

1. THE PROCESS OF PRODUCING A VULCANIZATE WHICH COMPRISES SULFUR-VULCANIZING A SULFUR-VULCANIZABLE HYUDROCARBONDIENE RUBBER IN THE PRESENCE OF A SMALL AMOUNT OF AN ANTIOZOME AGENT WHICH IS FROM THE CLASS CONSISTING OF COMPOUNDS HAVING THE FORMULAE. 